Extractant compositions for co-extracting cesium and strontium, a method of separating cesium and strontium from an aqueous feed, and calixarene compounds

Abstract

A mixed extractant solvent that includes at least one dialkyloxycalix[4]arenebenzocrown-6 compound, 4′,4′,(5′)-di-(t-butyldicyclohexano)-18-crown-6, at least one modifier, and, optionally, a diluent. The dialkyloxycalix[4]arenebenzocrown-6 compound is 1,3-alternate-25,27-di(octyloxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(decyloxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(dodecyloxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(2-ethylhexyl-1-oxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(3,7-dimethyloctyl-1-oxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(4-butyloctyl-1-oxy)calix[4]arenebenzocrown-6, or combinations thereof. The modifier is a primary alcohol. A method of separating cesium and strontium from an aqueous feed is also disclosed, as are dialkyloxycalix[4]arenebenzocrown-6 compounds and an alcohol modifier.

1. A mixed extractant solvent, comprising:
 at least one dialkyloxycalix[4]arenebenzocrown-6 compound selected from the group consisting of: 
 
       
         
           
           
               
               
           
         
       
       and combinations thereof;
 4′,4′,(5′)-di-(t-butyldicyclohexano)-18-crown-6; at least one modifier; and a diluent. 
 
     
     
       2. The mixed extractant solvent of  claim 1 , wherein the at least one modifier comprises at least one primary alcohol modifier. 
     
     
       3. The mixed extractant solvent of  claim 2 , wherein the at least one primary alcohol modifier comprises at least one alkylphenoxy ethyl alcohol lacking fluorine substituents, at least one alkylphenoxy propyl alcohol lacking fluorine substituents, or combinations thereof. 
     
     
       4. The mixed extractant solvent of  claim 2 , wherein the at least one primary alcohol modifier comprises 3-[4-(tert-octyl)phenoxy]-1-propanol, 3-[4-(sec-butyl)phenoxy]-1-propanol, 3- [4-(tert-octyl)phenoxy]-2-methyl-1-propanol, 3-[4-(sec-butyl)phenoxy]-2-methyl-1-propanol, or combinations thereof. 
     
     
       5. The mixed extractant solvent of  claim 2 , wherein the at least one primary alcohol modifier comprises a straight chain primary alcohol selected from the group consisting of 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, and combinations thereof. 
     
     
       6. The mixed extractant solvent of  claim 5 , wherein the at least one primary alcohol modifier comprises from 75% by weight to 85% by weight of C 9 , C 10 , and C 11  primary alcohols. 
     
     
       7. The mixed extractant solvent of  claim 2 , wherein the at least one primary alcohol modifier comprises a branched isomer of hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, or combinations thereof. 
     
     
       8. The mixed extractant solvent of  claim 7 , wherein the at least one primary alcohol modifier comprises methylpentanol, ethylbutanol, methylhexanol, ethylpentanol, methylheptanol, ethylhexanol, methyloctanol, ethylheptanol, methylnonanol, ethyloctanol, methyldecanol, ethylnonanol, methylundecanol, ethyldecanol, methyldodecanol, ethylundecanol, or combinations thereof. 
     
     
       9. The mixed extractant solvent of  claim 1 , wherein the mixed extractant solvent consists essentially of: 
       
         
           
           
               
               
           
         
         4′,4′,(5′)-di-(t-butyldicyclo-hexano)-18-crown-6; 
         3-[4-(sec-butyl)phenoxy]- 2 -methyl-1-propanol; and the diluent. 
       
     
     
       10. The mixed extractant solvent of  claim 1 , further comprising an amine. 
     
     
       11. A mixed extractant solvent, comprising:
 at least one dialkyloxycalix[4]arenebenzocrown-6 compound; 
 4′,4′,(5′)-di-(t-butyldicyclo-hexano)-18-crown-6; and 
 at least one modifier comprising an alkylphenoxy alcohol compound lacking fluorine
 substituents, wherein the alkylphenoxy alcohol compound is not 2-(4-tert-octylphenoxy)-1 -ethanol ,1-ethoxy-3-(4-tert-octylphenoxy)-2-propanol or 1-isopropoxy-3-(4-tert-octylphenoxy)-2-propanol. 
 
 
     
     
       12. A method of separating cesium and strontium from an aqueous feed, comprising:
 contacting an aqueous feed comprising cesium and strontium with a mixed extractant solvent,
 the mixed extractant solvent comprising: 
 at least one dialkyloxycalix[4]arenebenzocrown-6 compound; 
 4′,4′,(5′)-di-(t-butyldicyclo-hexano)-18-crown-6; and 
 at least one modifier comprising an alkylphenoxy alcohol compound lacking fluorine substituents, wherein the alkylphenoxy alcohol compound is not 2-(4-tert-octylphenoxy)-1-ethanol,1-ethoxy-3-(4-tert-octylphenoxy)-2-propanol or 1-isopropoxy-3-(4-tert-octylphenoxy)-2-propanol; and 
 
 removing the cesium and strontium from the aqueous feed. 
 
     
     
       13. The method of  claim 12 , wherein the at least one dialkyloxycalix[4]arenebenzocrown-6 compound comprises 1,3-alternate-25,27-di(octyloxy)calix[4]arenebenzocrown-6,1,3-alternate-25, 27-di(decyloxy)calix[4]arenebenzocrown-6,1,3-alternate-25,27-di(dodecyloxy) calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(2-ethylhexyl-1-oxy)calix[4]arene -benzocrown-6,1,3-alternate-25,27-di(3,7-dimethyloctyl-1-oxy)calix[4]arenebenzocrown-6, 1,3-alternate-25,27-di(4-butyloctyl-1-oxy)calix[4]arenebenzocrown-6, or combinations thereof. 
     
     
       14. The method of  claim 12 , wherein the at least one modifier comprises at least one alkylphenoxy ethyl alcohol lacking fluorine substituents, at least one alkylphenoxy propyl alcohol lacking fluorine substituents, or combinations thereof. 
     
     
       15. The method of  claim 12 , wherein the at least one modifier comprises 3-[4-(tert-octyl)phenoxy]-1-propanol, 3-[4-(sec-butyl)phenoxy]-1-propanol, 3-[4-(tert-octyl)phenoxy]-2-methyl-1-propanol, 3-[4-(sec-butyl)phenoxy]-2-methyl-1-propanol, or combinations thereof. 
     
     
       16. The method of  claim 12 , wherein the at least one modifier comprises 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, or combinations thereof. 
     
     
       17. The method of  claim 12 , wherein the at least one modifier comprises methylpentanol, ethylbutanol, methylhexanol, ethylpentanol, methylheptanol, ethylhexanol, methyloctanol, ethylheptanol, methylnonanol, ethyloctanol, methyldecanol, ethylnonanol, methylundecanol, ethyldecanol, methyldodecanol, ethylundecanol, or combinations thereof. 
     
     
       18. The method of  claim 12 , wherein contacting an aqueous feed comprising cesium and strontium with a mixed extractant solvent comprises contacting the aqueous feed with a mixed extractant solvent comprising from approximately 7mM to approximately 50 mM of the at least one dialkyloxycalix[4]arenebenzocrown-6compound, from approximately 10 mM to approximately 500 mM of 4′,4′,(5′)-di-(t-butyldicyclo-hexano)-18-crown-6, and from approximately 0.5 M to approximately 3.0 M of the at least one modifier. 
     
     
       19. The method of  claim 12 , wherein contacting an aqueous feed comprising cesium and strontium with a mixed extractant solvent comprises contacting the aqueous feed comprising a nitric acid concentration of from approximately 1.5 M to approximately 5 M with the mixed extractant solvent. 
     
     
       20. The method of  claim 12 , wherein contacting an aqueous feed comprising cesium and strontium with a mixed extractant solvent comprises extracting the cesium and strontium into the mixed extractant solvent. 
     
     
       21. A calixarene compound comprising: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
       22. A mixed extractant solvent, comprising:
 calix[4]arene-bis(tert-octylbenzo)-crown-6 (“BOBCalixC6”),4′,4′,(5′)-di-(t-butyldicyclo-hexano) -18-crown-6 (“DtBuCH18C6”),3-[4-(sec-butyl)phenoxy]-2-methyl-l-propanol, and a diluent.